CA2114035A1 - Process for preparing aqueous coating agents using modular systems - Google Patents
Process for preparing aqueous coating agents using modular systemsInfo
- Publication number
- CA2114035A1 CA2114035A1 CA002114035A CA2114035A CA2114035A1 CA 2114035 A1 CA2114035 A1 CA 2114035A1 CA 002114035 A CA002114035 A CA 002114035A CA 2114035 A CA2114035 A CA 2114035A CA 2114035 A1 CA2114035 A1 CA 2114035A1
- Authority
- CA
- Canada
- Prior art keywords
- special effect
- water
- module
- aqueous
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 91
- 239000011230 binding agent Substances 0.000 claims abstract description 89
- 239000004922 lacquer Substances 0.000 claims abstract description 52
- 239000000049 pigment Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 125000000129 anionic group Chemical group 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 230000003287 optical effect Effects 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims description 51
- 239000011347 resin Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 22
- 238000004132 cross linking Methods 0.000 claims description 17
- 238000000518 rheometry Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 229920005749 polyurethane resin Polymers 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 description 25
- 239000004814 polyurethane Substances 0.000 description 25
- 239000006185 dispersion Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 239000005056 polyisocyanate Substances 0.000 description 17
- 229920001228 polyisocyanate Polymers 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 229920002635 polyurethane Polymers 0.000 description 14
- 229920003009 polyurethane dispersion Polymers 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 7
- 229920006243 acrylic copolymer Polymers 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229920003180 amino resin Polymers 0.000 description 6
- -1 ether alcohols Chemical class 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000000159 acid neutralizing agent Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 description 1
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical compound CCCCOC(O)CC IDQBJILTOGBZCR-UHFFFAOYSA-N 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PEMPTAMMHPNASA-UHFFFAOYSA-M F[Li].[Mg].[Na] Chemical compound F[Li].[Mg].[Na] PEMPTAMMHPNASA-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000530268 Lycaena heteronea Species 0.000 description 1
- 241001082241 Lythrum hyssopifolia Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- JTDWCIXOEPQECG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC(C)(C)C Chemical compound N=C=O.N=C=O.CCCCCC(C)(C)C JTDWCIXOEPQECG-UHFFFAOYSA-N 0.000 description 1
- VDVJBLBBQLHKKM-UHFFFAOYSA-N OOP(=O)OO Chemical class OOP(=O)OO VDVJBLBBQLHKKM-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 150000004729 acetoacetic acid derivatives Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001046 green dye Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005903 polyol mixture Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical compound C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/067—Metallic effect
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
Abstract A process for preparing aqueous coating agents with adjustable optical effects by mixing at least two storage-stable pre-mixed aqueous modules (units) is described, in which A) at least one aqueous special effect module containing one or more special effect pigments, one or more anionic and/or non-ionic stabilised water-dilutable binders, one or more organic solvents, at least 20 wt.% of water and optionally conventional lacquer additives, and B) at least one aqueous binder module containing one or more anionic and/or non-ionic stabilised water-dilutable binders, water, and optionally one or more organic solvents, one or more cross-linking agents and/or conventional lacquer additives, are mixed together.
Description
211~35 A process for preparing aqueous coatin~ aqents using modular systems The invention relates to a process for preparing aqueous coating agents with adjustable optical effects using modular systems (mixing systems). It is suitable in particular for preparing long-term storage-stable aqueous special effect base lacquers which may bè used in particular for lacquering motor vehicles and motor vehicle parts.
The use of water-dilutable lacquer systems is steadily gaining acceptance in the motor vehicle and motor vehicle parts sector. There is a demand, especially in the area of aqueous special effect base lacquers, for a constantly increasing number of special effect shades, which renders efficient production and storage increasingly difficult. ~-One way to solve this problem is the provision of a limited number of storable individual units, which are combined, ~ ~ -depending on the desired special effect shade, to give the final, aqueous special effect base lacquer shortly before application.
Thus, EP-A-399 427 describes a water base lacquer modular system consisting of 5 units which, after combination, produce a final water base lacquer. In this case it is essential, according to the invention, that the special effect unit, the component with metal-containing pigments, must be prepared and stored in the absence of water. This is achieved by slurrying metal-containing pigments in an alkyd, acrylate or polyester resin dissolved in a solvent and an -organic solvent. Special effect units prepared in this way do not contain a neutralising agent for acid resins. The water base lacquers formulated therewith thus have an undesired high proportion of solvent and a separate neutralising unit is required. In addition, production of this water base lacquer requires strict observation of the mixing sequence for the individual units.
~ . , '' 2 2~1~035 Furthermore, aqueous lacquers based on different units are described in EP-A-0 468 293 and EP-A-0 471 972. However, it is essential that the special effect unit contains no water.
DE-A-41 10 520 describes a mixing system which is intended to be suitable for preparing aqueous pigmented coating agents with precisely determined shades. It is intended in particular for preparing water base lacquers. The mixing system consists of various basic dyes (A), which contain less than 5 wt.% of water, preferably no water, and pigments, solvents and water-dilutable binders, and a pigment-free aqueous component (B) which contains in particular water-dilutable binders and/or rheological additives. The water-dilutable binders contained in component A are present in solvent form and must be capable of being prepared in solvent form. The water base lacquers formulated in this way therefore have undesired high proportions of solvent. The final coating agents are prepared by mixing the components just before application, they are not storage-stable.
The object of the invention is the provision of a process for preparing aqueous coating agents, in particular for preparing aqueous single-component special effect base lacquers with low solvent contents using a modular system or mixing system or unit system which is stable over a long period of time, wherein the individual modules in the system can easily be mixed with each other in order to produce a desired special effect.
It has been shown that this object can be achieved by the use of a modularlsystem which contains a special effect module with a high water content.
The invention thus provides a process for preparing aqueous coating agents with adjustable optical effects by mixing at least two storage-stable pre-mixed aqueous modules, which is characterised in that 3 ~ 1 4~3~
A) at least one aqueous special effect module containing one or more special effect pigments, one or more water-dilutable anionic and/or non-ionic stabilised binders, one or more organic solvents, at least 20 wt.% of water and optionally conventional lacquer additives and B) at least one aqueous binder module containing one or more water-dilutable anionic and/or non-ionic stabilised binders, water, optionally one or more organic solvents, and optionally one or more cross-linking agents and/or~ ~ .
one or more conventional lacquer additives, are mixed together.
The modular system used according to the invention may contain, in addition to special effect module A) and binder :
module B), for example, :
C) at least one dye module containing one or more pigments and/or fillers, one or more anionic and/or non-ionic :
stabilised, water-dilutable binder and water, and ~
optionally one or more organic solvents and/or .
conventional lacquer additives, and/or -: D) at least one rheology module containing one or more organic or inorganic agents for regulating the rheology (rheology components) and water, and optionally one or more water-dilutable anionic and/or non-ionic stabilised binders and/or one or more organic solvents, and/or - ~ .
E) at least one cross-linking module containing one or more :.
'~ cross-linking agents and optionally one or more organic solvents, water, one or more anionic and/or non-ionic stabilised water-dilutable binders and/or one or more conventional lacquer additives.
,~
Here, modules are understood to be storage-stable units ~ :
(mixing units) which can be stored separately, from which a ~.
The use of water-dilutable lacquer systems is steadily gaining acceptance in the motor vehicle and motor vehicle parts sector. There is a demand, especially in the area of aqueous special effect base lacquers, for a constantly increasing number of special effect shades, which renders efficient production and storage increasingly difficult. ~-One way to solve this problem is the provision of a limited number of storable individual units, which are combined, ~ ~ -depending on the desired special effect shade, to give the final, aqueous special effect base lacquer shortly before application.
Thus, EP-A-399 427 describes a water base lacquer modular system consisting of 5 units which, after combination, produce a final water base lacquer. In this case it is essential, according to the invention, that the special effect unit, the component with metal-containing pigments, must be prepared and stored in the absence of water. This is achieved by slurrying metal-containing pigments in an alkyd, acrylate or polyester resin dissolved in a solvent and an -organic solvent. Special effect units prepared in this way do not contain a neutralising agent for acid resins. The water base lacquers formulated therewith thus have an undesired high proportion of solvent and a separate neutralising unit is required. In addition, production of this water base lacquer requires strict observation of the mixing sequence for the individual units.
~ . , '' 2 2~1~035 Furthermore, aqueous lacquers based on different units are described in EP-A-0 468 293 and EP-A-0 471 972. However, it is essential that the special effect unit contains no water.
DE-A-41 10 520 describes a mixing system which is intended to be suitable for preparing aqueous pigmented coating agents with precisely determined shades. It is intended in particular for preparing water base lacquers. The mixing system consists of various basic dyes (A), which contain less than 5 wt.% of water, preferably no water, and pigments, solvents and water-dilutable binders, and a pigment-free aqueous component (B) which contains in particular water-dilutable binders and/or rheological additives. The water-dilutable binders contained in component A are present in solvent form and must be capable of being prepared in solvent form. The water base lacquers formulated in this way therefore have undesired high proportions of solvent. The final coating agents are prepared by mixing the components just before application, they are not storage-stable.
The object of the invention is the provision of a process for preparing aqueous coating agents, in particular for preparing aqueous single-component special effect base lacquers with low solvent contents using a modular system or mixing system or unit system which is stable over a long period of time, wherein the individual modules in the system can easily be mixed with each other in order to produce a desired special effect.
It has been shown that this object can be achieved by the use of a modularlsystem which contains a special effect module with a high water content.
The invention thus provides a process for preparing aqueous coating agents with adjustable optical effects by mixing at least two storage-stable pre-mixed aqueous modules, which is characterised in that 3 ~ 1 4~3~
A) at least one aqueous special effect module containing one or more special effect pigments, one or more water-dilutable anionic and/or non-ionic stabilised binders, one or more organic solvents, at least 20 wt.% of water and optionally conventional lacquer additives and B) at least one aqueous binder module containing one or more water-dilutable anionic and/or non-ionic stabilised binders, water, optionally one or more organic solvents, and optionally one or more cross-linking agents and/or~ ~ .
one or more conventional lacquer additives, are mixed together.
The modular system used according to the invention may contain, in addition to special effect module A) and binder :
module B), for example, :
C) at least one dye module containing one or more pigments and/or fillers, one or more anionic and/or non-ionic :
stabilised, water-dilutable binder and water, and ~
optionally one or more organic solvents and/or .
conventional lacquer additives, and/or -: D) at least one rheology module containing one or more organic or inorganic agents for regulating the rheology (rheology components) and water, and optionally one or more water-dilutable anionic and/or non-ionic stabilised binders and/or one or more organic solvents, and/or - ~ .
E) at least one cross-linking module containing one or more :.
'~ cross-linking agents and optionally one or more organic solvents, water, one or more anionic and/or non-ionic stabilised water-dilutable binders and/or one or more conventional lacquer additives.
,~
Here, modules are understood to be storage-stable units ~ :
(mixing units) which can be stored separately, from which a ~.
4 ~ 0 ~ 5 final coating agent can be prepared by mixing, which optionally can still be adjusted to the application viscosity. By means of mixing the individual modules, deslred adjustable special effects, and optionally adjustable shades of colour, can be obtained. The modules could be provided by the manufacturer in the form of a set containing, for example, at least modules A) and B).
Different embodiments may be prepared from each of the modules A) to E). A set of modules is produced in this way which may consist of one or more modules.
Special effect module A) is an aqueous preparation which contains at least one special effect pigment, at least one water-dilutable resin (binder) and at least 20 wt.% of water, a proportion of organic solvents and optionally conventional lacquer additives.
Special effect pigments are those pigments which produce a decorative effect in lacquer coatings and also, but not exclusively, may produce a coloured effect. Special effect pigments are distinguished in particular by a plate-like structure. Examples of special effect pigments are: metallic pigments, e.g. made from aluminium, steel, copper or other metals; interference pigments such as e.g. metal oxide coated metallic pigments, e.g. titanium dioxide coated or mixed oxide coated aluminium, coated micas such as e.g. titanium dioxide coated mica and graphite effect pigments.
i~
number of these special effect pigments is available commerciallyfand they differ in particle size, particle size distribution and particle shape. The choice of pigment depends on the particular special effect desired in the lacquer film. Special effect modules with only one pigment are preferably prepared. However, it is also possible to prepare special effect modules which contain several different special effect pigments.
~ : ' .; ~ : , . , 3 ~
:
Surprisingly, it has been shown, within the scope of the invention, that aqueous modules containing special effect pigments, especially metallic pigments, may be provided for the process according to the invention, wherein the metallic pigments may even consist of water-sensitive metals such as aluminium or steel. It has been shown that this is possible in particular when the special effect module contains 3 to 13 wt.%, especially 3.5 to 4 wt.% of the water-sensitive metallic pigment. The pH is then preferably 7.2 to 8.0, particularly preferably 7.5 to 8Ø The pigment/binder ratio in this case is preferably 0.02 : l to 10 : 1, with reference to the weight of solids. Due to the provision of this type of aqueous special effect module based on metallic pigments, a lacquer material which has a particularly low solvent content can be provided by the process according to the invention.
The water-dilutable resins contained in the special effect module may carry an anionic charge. Anionic resins in the form of aqueous solutions or dispersions neutralised with bases are available.
~ ' The water-dilutable resins contained in the special effect module may also be non-ionically stabilised. For example, those resins which are described later for binder module B) may be used.
In the case of anionic resins, the anionic groups are preferably present as neutralised carboxyl groups, corresponding to an acid value of preferably 15 - 70 mg KOH/g. Aqueous special effect modules containing anionic resins preferably have a pH of 7.0 - 9Ø
The resins may be conventional film-forming binders and/or paste resins. They may be based, for example, on polyesters, ~ ~-polyacrylates or polyurethanes, as explained in the description of the set of binder modules. Preferably, ~2~4~3~
polyurethane resins are used as water-dilutable resins in the special effect module.
Water-dilutable or non-water-dilutable cross-linking components may also be contained in the special effect module. These cross-linking components are described in more detail in the description of the cross-linking module.
Preferably, each of the aqueous special effect pigment modules contains the same binder or binder mixture. This means that a constant binder composition can be produced, even when mixing different modules.
Furthermore, the special effect module may contain a small proportion of at least one water-miscible solvent, such as alcohols, e.g. monoalcohols such as butanol, n-propanol or isopropanol; ether alcohols, e.g. butoxyethanol, butoxypropanol or methoxypropanol; dialcohols such as glycols, e.g. ethylene glycol, polyethylene glycol;
trialcohols such as glycerol; ketones, e.g. acetone, methylethyl ketone or N-methylpyrrolidone; ethers, e.g.
dipropyleneglycol dimethyl ether.
The special effect module preferably contains a rheology regulating agent. These may be the substances or mixtures which are described for the preparation of a rheology module.
These may be directly added during preparation of the special effect module or admixed later as a finished rheology module.
.
Furthermore, conventional lacquer additives such as e.g, wetting agents, defoamers, neutralising agents and catalysts may be contained in the aqueous special effect module.
:
The aqueous special effect module is generally prepared in such a way that the special effect pigment, e.g. in the form -of a commercially available paste, is initially introduced, water-dilutable solvent and additives are added and then the ' :~
' ~' ' ~: - . .
i,, , . . :
. . .
- 2~1~035 aqueous resin solution is admixed under a shear force.
Powdery special effect pigments are first processed with solvent and additives to produce a paste. Care should be taken that platelet-shaped special effect pigments are not mechanically damaged during the mixing process.
Aqueous storage-stable special effect modules with a preferred pigment/binder ratio of 0.02 : 1 to 10 : 1 are produced. The solids content of the whole special effect module is then preferably 10 to 40 wt.%. The ratio by weight of water to organic solvent in the aqueous special effect module is preferably 12 : 1 to 3 : 1. The water content of the special effect module is at least 20, preferably 20 to 75 wt.%.
Binder B) is an aqueous solution or dispersion of at least one anionic and/or non-ionic stabilised water-dilutable binder. These are film-forming resins or paste resins such as are normally used in aqueous coating agents, especially in aqueous base lacquers. They may be present alone or in combination. The film-forming resins may be based on polyesters, polyacrylates or preferably polyurethanes. They may be self-cross-linked or require an external cross-linking agent or dry out physically.
Examples of suitable non-ionically stabilised binders are those binders whose water-dilutability is achieved by the incorporation of polyether segments into the resin molecule.
Examples of this type of stabilised polyurethane or polyurethanacrylate resin are described in EP-A-354 261, EP-A-422 357 and EP-A-424 705.
The aqueous binder module preferably contains anionic stabilised binders. Examples of these are (meth)acrylic copolymers, polyester resins or preferably polyurethane resins.
,' ~
~` ~114~35 Examples of suitable water-dilutable (meth)acrylic copolymers can be found in EP-A-399 427 and EP-A-287 144.
Examples of suitable water-dilutable polyester resins are described in DE-A-29 26 584, DE-A-38 32 142 and EP-A-301 300.
It is also possible to use mixtures of such binders.
Particularly suitable binders are those in which (meth)acrylic copolymers and polycondensation resin are present bonded covalently or in the form of interpenetrating resin molecules. Examples of these resins as this type of combination of (meth)acrylic copolymers and polyester resin are described in EP-A-226 171.
Examples of the particularly preferred anionic stabilised polyurethane resins are described in great variety in the literature. These are aqueous polyurethane dispersions or solutions or those binders in which (meth)acrylic copolymers and polyurethane resin are present bonded covalently or in the form of interpenetrating resin molecules. Suitable PU
dispersions are stable, aqueous dispersions with a solids content of 20 to 50%. The molecular weight (Mw) of the resins may vary over wide limits, from 1000 to 500000, wherein the molecular weights of film-forming binders lie in the upper range of numbers and those of paste resins lie in the lower range of numbers.
.
Examples of polyurethane dispersions which may be prepared by chain-lengthening prepolymers which contain isocyanate functions using polyamines and/or polyols, are found in EP-A-89 497, EP-A'228 003, DE-A-36 28 124 and EP-A-512 524.
, : :
Polyurethane dispersions which may be prepared by chain-lengthening prepolymers which contain isocyanate functions using water are described in DE-A-39 15 459.
': ' . ' ~
., : ~,,; ~ ~ .
3 ~
Particularly preferred polyurethane dispersions of this type are described in P 42 24 617, from the same applicant, which has not yet been laid open for public inspection. These are self-emulsifying polyurethane dispersions which preferably have an acid value, with reference to the solids content, in the non-neutralised state, of 5 to 50, particularly preferably of more than 10 and less than 30. The self-emulsifying urethane resin preferably has a glass transition temperature which is lower than the dispersing temperature.
The dispersion may be prepared in such a way that, e.g. a urethane prepolymer is prepared by reacting one or more polyisocyanates (a), preferably diisocyanates, with a polyetherdiol or polyesterdiol (bl) or a mixture thereof, and optionally one or more low-molecular weight polyhydroxyl compounds (b2) and one or more dimethylolalkanoic acids (c) in a NCO/OH ratio by -~
equivalents of 1.1-2.0 : l, preferably 1.1 - 1.9 : l, in a single or multi-stage reaction in a hydrophilic organic solvent which contains no active hydrogens. Subsequently chain-lengthening with water takes place, for example in the organic phase, wherein for example 0.5 to 3 moles of water are used per NCO group. The polymers thus obtained may be emulsified in further water after or during neutralisation with an amine and the organic solvent may be distilled off, if necessary.
, Examples of polyurethane dispersions which are prepared by chain-lengthening of PU prepolvmers which contain active hydrogens which react with polyisocyanates, using polyisocyanates, may be found in DE-A-39 03 804 and DE-A-40 01 841.
~11403~
Further anionic stabilised polyurethane ~PU) dispersions are described in P 42 28 510, from the same applicant, which has not yet been laid open to public inspection. These are aqueous polyurethane resin dispersions which are obtainable by chain-lengthening of - one or more polyurethane resins which contain at least one CH-acid group in the molecule by reaction in aqueous or non-aqueous medium with - at least one compound which can react with at least two CH-acid groups and - optional transfer of a reaction product obtained in non-aqueous medium to the aqueous phase.
The dispersions are preferably prepared solvent-free. The binder preferably still contains reactive functional groups.
The polyurethane resin which contains at least one CH-acid group may be prepared by a variety of methods. This type of CH-acid PU resin is described, for example, in EP-A-0 367 051.
.; .
Another method for preparing a dispersion of this type of polyurethane resin is to react a polyurethane resin with at least one ionic group whiah contains OH groups, which may contain urea groupings, in an anhydrous medium, with at least one compound which has at least one functional group which is suitable for reaction with at least some of the OH groups in theipolyurethàne resin and in addition contains a CH-acid group and transferring the product obtained to the aqueous phase after neutralisation.
The chains in the dispersions are lengthened before or after transfer to the aqueous phase using a compound which can '' , ,_~ S~ 0 3 ~
ll react with two CH-acid functions. Pre~erably, however, chain-lengthening is performed in aqueous dispersion.
Compounds suitable for chain-lengthening are those which can react with CH-acid centres. At least a two-fold possibility of reaction must be provided. Examples of such compounds are aldehydes or di- or polyisocyanates. Appropriate chain-lengthening reagents may be used separately or in combination.
Examples of anionic stabilised polyurethane-based binders which are suitable as a component of the aqueous binder module in which (meth)acrylic copolymers and polyurethane resin, bonded covalently or in the form of interpenetrating resin molecules, are present are described, for example, in EP-A-353 797, EP-A-297 576, DE-A-41 22 265 and DE-A-41 22 266. These are polymer hybrids which are prepared by emulsion polymerisation of radically polymerisable monomers in the presence of anionic stabilised polyurethanes which optionally -carry unsaturated functions.
These are preferably the type of polyurethane based binder described in DE-A-41 22 265.
These are polyurethane dispersions, prepared by radical-initiated polymerisation of polyurethane macromonomers with a proportion of carboxyl, phosphonic acid or sulphonic acid groups and lateral vinyl groups as well as optional terminal vinyl groups, hydroxyl, urethane, thiourethane and/or urea groups.
These polyurethane dispersions may, in principle, be prepared by a variety of methods. One method comprises, e.g. preparing a polyaddition product by polyaddition of polyhydroxy compounds from the group polyhydroxy-polyethers, polyhydroxy-polyesters and polyhydroxy-polycarbonates, also polyhydroxycarboxylic acids, dihydroxyphosphonic acids or ;~ ~ ;
.
: .
4~3~
polyhydroxysulphonic acids as well as polyisocyanates and a monomer which contains at least two hydroxyl groups and at least one vinyl group. The proportions of reactants, in particular of polyisocyanate, are selected so that a macromonomer with terminal hydroxyl groups is produced. This macromonomer, which in addition contains carboxyl, phosphonic acid or su~phonic acid groups and lateral vinyl groups, is then neutralised, if the acid groups in the monomers which contained these groups were not used initially in the neutralised form.
To prepare the polyurethane dispersion, the macromonomers thus obtained, which contain vinyl groups, are converted into an aqueous dispersion by the addition of water and polymerised by radical-initiated polymerisation using methods which are known per se. During this polymerisation, if so-called reactive diluters are not present from the start, monomers are added which are then co-polymerised into the polyurethane.
These monomers are alpha,beta-unsaturated monomers. Examples of these are alpha,beta-unsaturated vinyl monomers such as alkylacrylates, -methacrylates and -crotonates with 1 to 20 carbon atoms in the alkyl chain, di-, tri- and tetraacrylates, -methacrylates and -crotonates of glycols, tri- and tetra-functional alcohols, substituted and unsubstituted acryl- and methacrylamides, vinylethers, alpha,beta-unsaturated aldehydes and ketones, vinylalkyl ketones with 1 to 20 carbon atoms in the alkyl chain, vinyl ethers, vinylesters, diesters of alpha,beta-unsaturated dicarboxylic acids, styrene, styrene derivatives, such as e.g, alpha-methylstyrene.
The polyurethane paste resins which are mentioned above, e.g.
from DE-A-40 00 889, may also be used as anionic stabilised PU resins in the aqueous binder module B) according to the invention. These are urethanised oil-free polyesters which '''~
' .
~21~4035 contain OH groups, prepared by reacting diisocyanates with an excess of a polyol mixture and lower molecular dialcohols, of which some also contain at least one acid group capable of forming an anion. The number average of the molecular mass of these PU binders is preferably 3000 to 200000, particularly preferably less than 50000.
The binder module B) needed to prepare aqueous base lacquers may consist of one aqueous binder. The aqueous binders may also, however, be present in combination. Thus, the binders are each prepared separately and stored as a single module afterwards or they are prepared as a mixture of binders and then stored as a multi-component binder module.
The binder module B) preferably contains aqueous binders based on anionic stabilised polyurethanes. It may be expedient, if some, e.g. up to 50 wt.% of the PU binder, is replaced by resins based on a combination of (meth)acrylic copolymer and polyester resin.
Furthermore, binder module B) may contain water-dilutable binders based on cellulose.
Aqueous binder module B) may also contain amino resins and/or blocked polyisocyanates. The amino resins and blocked polyisocyanates may be water-dilutable or non-water-dilutable and are commented on under the description of the cross-linking module. They are present in a ratio of 40 : 60 to 5 : 95 with respect to the water-dilutable binder, each being with reference to the solid resin.
I I
Rheology regulating agents may also be contained.
Furthermore, the aqueous binder may contain small proportions of conventional solvents, preferably less than 5 wt.%. These may be the water-miscible solvents described for the special effect module. The solids content of the binder module is preferably 20 to 60 wt.%.
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The binder module B) may contain neutralisation agents for the anionic resins. Bases are used for this. Examples are ammonia or organic amines such as triethylamine, N-methylmorpholine, aminoalcohols such as dimethyl-isopropanolamine, dimethylethanolamine, 2-amino-2-methylpropanol-l.
Aqueous binder module units which contain anionic resins have a pH of 7.0 - 8.5. The ratio of organic solvent to water in the aqueous binder module is up to 0.3 : 1, preferably less than 0.2 : 1.
The modular system (made from modules A) and B)) used according to the invention may also include at least one aqueous dye module C), which contains, in addition to at least one anionic and/or non-ionic stabilised water-dilutable ~-binder, dye pigments and/or fillers and optionally additives.
Each dye module C) preferably contains not more than 4 different dye pigments and/or fillers, particularly preferred aqueous dye modules being those which contain only one dye pigment or only one filler. Examples of inorganic or organic dye pigments or fillers which can be used in the dye module are titanium dioxide, micronised titanium dioxide, iron oxide pigments, carbon black, silicon dioxide, barium sulphate, micronised mica, talc, azo-dyes, phthalocyanin dyes, quinacridone or pyrrolopyrrole pigments.
The same water-dilutable anionic and/or non-ionic stabilised resins may be used as described for the binder module. These are preferably binders which carry an anionic charge which act!as binder components in the final special effect base lacquer. The resins may be based on polyesters, acrylates or polyurethanes. The resins may be paste resins alone or in combination with film-forming binders or cross-linking agents. PU paste resins, as described in DE-A-40 00 889, are particularly preferred.
::
~114035 Each aqueous dye module C) preferably contains the same binder or mixture of binders. In addition, water-dilutable or non-water-dilutable cross-linking component~ may be contained in the dye module.
Furthermore, the dye module C) may contain small proportions of water-miscible solvents. Bases may also be contained as neutralisation agents. It may be convenient if dye module C) contains rheology regulating agents. Furthermore, conventional lacquer additives, such as e.g. wetting agents, defoamers and flow controllers, may be contained in aqueous dye module C).
The aqueous dye modules C) are generally prepared in such a way that the dye pigment or filler is ground into some of the aqueous binder or preferably into a paste resin. This takes place in equipment which is known to the person skilled in the art. Afterwards, the remaining amount of water-dilutable resin is added. This may be the same or a different binder from that used in the dispersing stage.
Aqueous, storage-stable dye modules C) are produced with a pigment/binder ratio of 0.01 : 1 to 10 : 1. The solids content is preferably 20 to 80 wt.%.
Dye modules which contain anionic resins have a pH of 7.0 to 10Ø The ratio of organic solvent to water in the aqueous dye modules is up to 0.3 : 1, preferably up to 0.2 : 1.
The modular system used according to the invention may contain a rheology module D). This contains water and one or more substances which regulate the flow behaviour of the final special effect base lacquer as a rheology component.
Examples of these are polymeric microparticles, such as are described, for example, in EP-A-38 127, inorganic sheet silicates, e.g. aluminium magnesium silicate, sodium r', ., .` . , r': ~ :
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magnesium sheet silicate and sodium magnesium fluorolithium sheet silicates of the montmorillonite type, associative thickeners, based on e.g. polyurethane or cellulose, polyvinylalcohols, synthetic polymers with ionic groups such as e.g. poly(meth)acrylic acid. These substances are commercially obtainable in a variety of forms.
. , The modular system used according to the invention may also contain a cross-linking module E). The cross-linking module E) is used in particular when the final aqueous special effect base lacquer being produced is being prepared with the use of resins which contain cross-linkable groups in the molecule.
Examples of cross-linking resins contained in the cross-linking module are amino resins and/or blocked isocyanates. -These are partially or completely etherified amine/
formaldehyde condensation resins and/or blocked polyisocyanates with at least two reactive sites per molecule. -Such amino resins are described, for example, in Ullmann's "Encyclopedia of Industrial Chemistry", 5th ed., vol, A2, chapter "Amino resins", pages 115 - 141 (1985) and Houben- ~ -Weyl, "Methoden der Organischen Chemie", vol. 14/2, pages 319 - 388 (1962). The resins are prepared according to the prior art and supplied by many firms as commercial products.
~ ~ .
Examples of such amino resins are amine/formaldehyde condensation resins which are produced by the reaction of aldehydes wlth melamine, guanamine, benzoguanamine or dicyanodiamide. The alcohol groups in the aldehyde condensation products are then partially or completely etherified with alcohols.
Examples of blocked isocyanates are any di- and/or ~ `
polyisocyanates in which the isocyanate groups have been : ,.,,.~-.
- ., .
17 2~ 3~
reacted with a compound which contains active hydrogen.
Appropriate prepolymers which contain isocyanate groups may also be used as di- and/or polyisocyanates. The organic di-and/or polyisocyanates have an average molecular weight of 112 to 2000 and expediently an average isocyanate functionality of 2 to 8. These are e.g. aliphatic, cycloaliphatic, aromatic, optionally also sterically hindered polyisocyanates. So-called "lacquer polyisocyanates" which are prepared from known diisocyanates are particularly suitable as polyisocyanates.
Typical examples of this type of polyisocyanate are propylene diisocyanate, tetramethylxylylene diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, trimethylhexane diisocyanate, cyclohexene-1,3 and -1,4 diisocyanate, methylcyclohexane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate or dicyclohexylmethane ~-diisocyanate.
Isocyanates which are convenient to use are polyisocyanates which also have urethane groups, which can be obtained by reacting excess amounts of diisocyanate with simple polyhydric alcohols with a molecular weight of 62 to 300, especially trimethylolpropane.
Lower molecular weight compounds for blocking NCO groups are ~ -known. Examples of these are aliphatic or cycloaliphatic alcohols, dialkylamino alcohols, oximes, lactams, imides, hydroxyalkyl esters, malonates or acetoacetates.
The cross-linking module may contain the cross-linking agent alone. However, it may also contain one or more organic solvents, water, one or more anionic and/or non-ionic stabilised, water-dilutable binders and/or one or more conventional lacquer additives. These are, for example, the same as those described for the other modules.
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18 ~1~403~
The different modules are storage-stable. They may be u~ed in the modular system according to the invention. Furthermore, it is possible to mix several identical or different modules to give new storage-stable combination modules. For example, different special effect and/or dye modules may be mixed.
Likewise, cross-linking modules and binder modules may be mixed. Likewise, the rheology module may be mixed with the special effect or the dye module. It has been shown to be expedient to select a modular system for mixing coating agents in which the special effect module and binder module and optionally the dye module are kept as separate entities.
The rheology and/or cross-linking module may be present as separate entities or mixed with the other modular units.
The aqueous single component special effect base lacquer is prepared by simply mixing the special effect module with the binder module and optionally the dye module and/or the rheology module and/or the cross-linking module. Any sequence may be used for admixing, preferably, however, the module with the highest viscosity and the largest share of the volume is initially introduced. After mixing well, the application viscosity is adjusted by the addition of deionised water.
The final special effect base lacquer prepared according to ~ ~;
the invention has a solids content of preferably 10 -40 wt.%, partiaularly preferably 15 - 30 wt.%, with a pigment/binder ratio of 0.06 : 1 to 0.6 : 1. The resin composition in the lacguer solids is preferably kept constant in each individual special effect base lacquer, wherein in thelcase of those special effect base lacquers which contain cross-linking agents there is a ratio of film-forming binder to cross-linking resins of 95 : 5 to 60 : 40 within the solid resin composition.
The proportion of solvent is less than 20 wt.%, preferably less than lO wt.%. The pH of the aqueous base lacquer is the ;
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19 '~1~ 4~3~
result of mixing the modular units. A correction to the pH i8 generally not required.
The final aqueous special effect base lacquer may be applied directly after mixing, but if may also be stored for longer than 12 months.
The aqueous special effect base lacquers prepared according to the invention may be applied using conventional methods.
They are preferably applied by spraying in a dry layer thickness of 10 - 25 ~m and processed using a wet-on-wet method, that is they are over-lacquered after an evaporation phase at 20 - 80C, using a conventional clear lacquer in a dry layer thickness of preferably 30 - 60 ~m, and dried or cross-linked in common with this at temperatures between 20 ~-and 140C.
The multi-layered special effect lacquers obtained in this way correspond to the currently conventional requirements for motor vehicle lacquers. The aqueous special effect base lacquers prepared according to the invention are thus suitable for lacquering vehicles and vehicle repairs, but they may also be used in other areas, such as e.g. lacquering plastics, in particular for lacquering motor vehicle parts.
The modular system used according to the invention consists of individual storage-stable modules. The modules contain film-forming binders which can be prepared in solvent form or in the agueous phase. Low-solvent, aqueous, special effect base lacquers which have good long-term storage stability, canlbe prepared using the modular system used according to the invention, In particular, efficient storage and production of the aqueous special effect base lacquer is achieved.
The following examples explain the invention. All parts (P) refer to parts by weight.
; , .
~ 35 Example 1 Preparation of a PU dispersion in accordance with DE patent application P 42 24 617, which is not yet laid open to public inspection, preparation example 3:
1005 g of a linear polyester (formed from adipic acid, isophthalic acid and hexanediol with an OH value of 102) are heated to 90C in a reaction vessel with a stirrer, internal thermometer, heat-supply and reflux condenser and 1.8 g of trimethylolpropane and 393 g of isophorone diisocyanate are added at this temperature. The mix is held at this temperature until the NCO value is 3.8. After cooling to ~ -60C, a solution of 35.3 g of dimethylolpropionic acid, 26.1 g of triethylamine and 250 g of N-methylpyrrolidone are added. After heating to 80C, the temperature is kept ~ -constant until an NCO value of 1.5 is reached. The molar amount of deionised water is admixed and the solution is held at 80C until isocyanate can no longer be detected. Finally, the mix is diluted with enough water to produce a liquid dispersion with a solids content of 34 wt.%.
., .
Example 2 ' -.
Preparation of a special effect module A
.
The following components are contained in the special effect module:
.`'' ' .
32.0 parts of a conventional polyurethane dispersion (in accordance with DE-A-4122265, example 1) with 35 wt.%
SC (SC = solids content), 13.4 parts of a commercially available aluminium paste containing 60 % aluminium, suitable for water base lacquers, 1.3 parts of an aluminium wetting additive based on organic phosphoric acid derivatives, ?~
21 ~114035 7.7 parts of n-butanol, 3.3 parts of a commercially available thickener based on polyacrylic acid, 3.3 parts of N,N-dimethylethanolamine.
The aluminium paste is initially introduced and mixed into a slurry with the solvent and additives. The binder is then added and mixed well.
Example 3 Preparation of a special effect module B
35 parts of the PU dispersion from example 1, 20 parts of the aluminium paste from example 2, 2 parts of the wetting additive from example 2, 25 parts of butyl glycol, 1.8 parts of the thickener from example 2 and 0.2 parts of N,N-dimethylethanolamine are processed using the same method as in example 2. Afterwards, the mixture is diluted with 16 parts of deionised water.
Example 4 PrepaFation of a binder module A
The following components are well mixed toqether with stlrring:
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42.0 parts of a conventional polyurethane dispersion (in accordance with DE-A-4122265, example 1) with 35% SC, 47.0 parts of completely demineralised water, 2.3 parts of n-butanol, 6.0 parts of butyl glycol, 1.4 parts of a commercially available thickener based on polyacrylic acid, 1.3 parts of N,N-dimethylethanolamine.
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Example 5 Preparation of a binder module B
26.2 parts of the PU dispersion from example 1, 8.8 parts of hexamethoxymethylmelamine, 5 parts of n-butanol, 3.5 parts of the thickener from example 2, 0.25 parts of N,N-dimethylethanolamine and 56.25 parts of deionised water were mixed together in the same way as in example 4.
Example 6 Preparation of a blue dye module A
The dye module contains the following components:
42.0 parts of a conventional polyurethane paste resin (in accordance with DE-A-4000889) with 35~ SC, 34.0 parts of a commercial blue copper phthalocyanine pigment, 5.0 parts of a dispersion aid (Disperse Ayd W22), 18. 85 parts of completely demineralised water, 0.15 parts of N,N-dimethylethanolamine.
First, the pigment is made into a slurry in a mixture of additives and about half of the paste resin. Then the rest of the paste resin, amine and water are added and well mixed.
':
Example 7 Preparation of a green dye module B
45 parts of the paste resin from example 6, 30 parts of a commercially available green phthalocyanine pigment, 5 parts of the dispersion aid from example 6, 2 parts of butyl glycol, 17.9 parts of deionised water and 0.1 parts of N,N-^ 211403~
dimethylethanolamine are processed in the same way as inexample 6.
Example 8 Preparation of aqueous special effect base lacquers Storage-stable special effect base lacquers are prepared by smoothly stirring together the modules cited in the Table:
SPECIAL EFFECT BASE LACQUERS
A (~ilver B (~ilver C (blue D ( green metallic) metallic) metallic) metallic) 8inder module A 70 P 60 P
Binder module B 80 P 75 P
Sp. effect mod. A 30 P 20 P
Sp. effect mod. B 20 P 15 P
Dye module A 20 P
Dye module B
P = parts by weight ;
.: . . . ~
Different embodiments may be prepared from each of the modules A) to E). A set of modules is produced in this way which may consist of one or more modules.
Special effect module A) is an aqueous preparation which contains at least one special effect pigment, at least one water-dilutable resin (binder) and at least 20 wt.% of water, a proportion of organic solvents and optionally conventional lacquer additives.
Special effect pigments are those pigments which produce a decorative effect in lacquer coatings and also, but not exclusively, may produce a coloured effect. Special effect pigments are distinguished in particular by a plate-like structure. Examples of special effect pigments are: metallic pigments, e.g. made from aluminium, steel, copper or other metals; interference pigments such as e.g. metal oxide coated metallic pigments, e.g. titanium dioxide coated or mixed oxide coated aluminium, coated micas such as e.g. titanium dioxide coated mica and graphite effect pigments.
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number of these special effect pigments is available commerciallyfand they differ in particle size, particle size distribution and particle shape. The choice of pigment depends on the particular special effect desired in the lacquer film. Special effect modules with only one pigment are preferably prepared. However, it is also possible to prepare special effect modules which contain several different special effect pigments.
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Surprisingly, it has been shown, within the scope of the invention, that aqueous modules containing special effect pigments, especially metallic pigments, may be provided for the process according to the invention, wherein the metallic pigments may even consist of water-sensitive metals such as aluminium or steel. It has been shown that this is possible in particular when the special effect module contains 3 to 13 wt.%, especially 3.5 to 4 wt.% of the water-sensitive metallic pigment. The pH is then preferably 7.2 to 8.0, particularly preferably 7.5 to 8Ø The pigment/binder ratio in this case is preferably 0.02 : l to 10 : 1, with reference to the weight of solids. Due to the provision of this type of aqueous special effect module based on metallic pigments, a lacquer material which has a particularly low solvent content can be provided by the process according to the invention.
The water-dilutable resins contained in the special effect module may carry an anionic charge. Anionic resins in the form of aqueous solutions or dispersions neutralised with bases are available.
~ ' The water-dilutable resins contained in the special effect module may also be non-ionically stabilised. For example, those resins which are described later for binder module B) may be used.
In the case of anionic resins, the anionic groups are preferably present as neutralised carboxyl groups, corresponding to an acid value of preferably 15 - 70 mg KOH/g. Aqueous special effect modules containing anionic resins preferably have a pH of 7.0 - 9Ø
The resins may be conventional film-forming binders and/or paste resins. They may be based, for example, on polyesters, ~ ~-polyacrylates or polyurethanes, as explained in the description of the set of binder modules. Preferably, ~2~4~3~
polyurethane resins are used as water-dilutable resins in the special effect module.
Water-dilutable or non-water-dilutable cross-linking components may also be contained in the special effect module. These cross-linking components are described in more detail in the description of the cross-linking module.
Preferably, each of the aqueous special effect pigment modules contains the same binder or binder mixture. This means that a constant binder composition can be produced, even when mixing different modules.
Furthermore, the special effect module may contain a small proportion of at least one water-miscible solvent, such as alcohols, e.g. monoalcohols such as butanol, n-propanol or isopropanol; ether alcohols, e.g. butoxyethanol, butoxypropanol or methoxypropanol; dialcohols such as glycols, e.g. ethylene glycol, polyethylene glycol;
trialcohols such as glycerol; ketones, e.g. acetone, methylethyl ketone or N-methylpyrrolidone; ethers, e.g.
dipropyleneglycol dimethyl ether.
The special effect module preferably contains a rheology regulating agent. These may be the substances or mixtures which are described for the preparation of a rheology module.
These may be directly added during preparation of the special effect module or admixed later as a finished rheology module.
.
Furthermore, conventional lacquer additives such as e.g, wetting agents, defoamers, neutralising agents and catalysts may be contained in the aqueous special effect module.
:
The aqueous special effect module is generally prepared in such a way that the special effect pigment, e.g. in the form -of a commercially available paste, is initially introduced, water-dilutable solvent and additives are added and then the ' :~
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- 2~1~035 aqueous resin solution is admixed under a shear force.
Powdery special effect pigments are first processed with solvent and additives to produce a paste. Care should be taken that platelet-shaped special effect pigments are not mechanically damaged during the mixing process.
Aqueous storage-stable special effect modules with a preferred pigment/binder ratio of 0.02 : 1 to 10 : 1 are produced. The solids content of the whole special effect module is then preferably 10 to 40 wt.%. The ratio by weight of water to organic solvent in the aqueous special effect module is preferably 12 : 1 to 3 : 1. The water content of the special effect module is at least 20, preferably 20 to 75 wt.%.
Binder B) is an aqueous solution or dispersion of at least one anionic and/or non-ionic stabilised water-dilutable binder. These are film-forming resins or paste resins such as are normally used in aqueous coating agents, especially in aqueous base lacquers. They may be present alone or in combination. The film-forming resins may be based on polyesters, polyacrylates or preferably polyurethanes. They may be self-cross-linked or require an external cross-linking agent or dry out physically.
Examples of suitable non-ionically stabilised binders are those binders whose water-dilutability is achieved by the incorporation of polyether segments into the resin molecule.
Examples of this type of stabilised polyurethane or polyurethanacrylate resin are described in EP-A-354 261, EP-A-422 357 and EP-A-424 705.
The aqueous binder module preferably contains anionic stabilised binders. Examples of these are (meth)acrylic copolymers, polyester resins or preferably polyurethane resins.
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~` ~114~35 Examples of suitable water-dilutable (meth)acrylic copolymers can be found in EP-A-399 427 and EP-A-287 144.
Examples of suitable water-dilutable polyester resins are described in DE-A-29 26 584, DE-A-38 32 142 and EP-A-301 300.
It is also possible to use mixtures of such binders.
Particularly suitable binders are those in which (meth)acrylic copolymers and polycondensation resin are present bonded covalently or in the form of interpenetrating resin molecules. Examples of these resins as this type of combination of (meth)acrylic copolymers and polyester resin are described in EP-A-226 171.
Examples of the particularly preferred anionic stabilised polyurethane resins are described in great variety in the literature. These are aqueous polyurethane dispersions or solutions or those binders in which (meth)acrylic copolymers and polyurethane resin are present bonded covalently or in the form of interpenetrating resin molecules. Suitable PU
dispersions are stable, aqueous dispersions with a solids content of 20 to 50%. The molecular weight (Mw) of the resins may vary over wide limits, from 1000 to 500000, wherein the molecular weights of film-forming binders lie in the upper range of numbers and those of paste resins lie in the lower range of numbers.
.
Examples of polyurethane dispersions which may be prepared by chain-lengthening prepolymers which contain isocyanate functions using polyamines and/or polyols, are found in EP-A-89 497, EP-A'228 003, DE-A-36 28 124 and EP-A-512 524.
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Polyurethane dispersions which may be prepared by chain-lengthening prepolymers which contain isocyanate functions using water are described in DE-A-39 15 459.
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Particularly preferred polyurethane dispersions of this type are described in P 42 24 617, from the same applicant, which has not yet been laid open for public inspection. These are self-emulsifying polyurethane dispersions which preferably have an acid value, with reference to the solids content, in the non-neutralised state, of 5 to 50, particularly preferably of more than 10 and less than 30. The self-emulsifying urethane resin preferably has a glass transition temperature which is lower than the dispersing temperature.
The dispersion may be prepared in such a way that, e.g. a urethane prepolymer is prepared by reacting one or more polyisocyanates (a), preferably diisocyanates, with a polyetherdiol or polyesterdiol (bl) or a mixture thereof, and optionally one or more low-molecular weight polyhydroxyl compounds (b2) and one or more dimethylolalkanoic acids (c) in a NCO/OH ratio by -~
equivalents of 1.1-2.0 : l, preferably 1.1 - 1.9 : l, in a single or multi-stage reaction in a hydrophilic organic solvent which contains no active hydrogens. Subsequently chain-lengthening with water takes place, for example in the organic phase, wherein for example 0.5 to 3 moles of water are used per NCO group. The polymers thus obtained may be emulsified in further water after or during neutralisation with an amine and the organic solvent may be distilled off, if necessary.
, Examples of polyurethane dispersions which are prepared by chain-lengthening of PU prepolvmers which contain active hydrogens which react with polyisocyanates, using polyisocyanates, may be found in DE-A-39 03 804 and DE-A-40 01 841.
~11403~
Further anionic stabilised polyurethane ~PU) dispersions are described in P 42 28 510, from the same applicant, which has not yet been laid open to public inspection. These are aqueous polyurethane resin dispersions which are obtainable by chain-lengthening of - one or more polyurethane resins which contain at least one CH-acid group in the molecule by reaction in aqueous or non-aqueous medium with - at least one compound which can react with at least two CH-acid groups and - optional transfer of a reaction product obtained in non-aqueous medium to the aqueous phase.
The dispersions are preferably prepared solvent-free. The binder preferably still contains reactive functional groups.
The polyurethane resin which contains at least one CH-acid group may be prepared by a variety of methods. This type of CH-acid PU resin is described, for example, in EP-A-0 367 051.
.; .
Another method for preparing a dispersion of this type of polyurethane resin is to react a polyurethane resin with at least one ionic group whiah contains OH groups, which may contain urea groupings, in an anhydrous medium, with at least one compound which has at least one functional group which is suitable for reaction with at least some of the OH groups in theipolyurethàne resin and in addition contains a CH-acid group and transferring the product obtained to the aqueous phase after neutralisation.
The chains in the dispersions are lengthened before or after transfer to the aqueous phase using a compound which can '' , ,_~ S~ 0 3 ~
ll react with two CH-acid functions. Pre~erably, however, chain-lengthening is performed in aqueous dispersion.
Compounds suitable for chain-lengthening are those which can react with CH-acid centres. At least a two-fold possibility of reaction must be provided. Examples of such compounds are aldehydes or di- or polyisocyanates. Appropriate chain-lengthening reagents may be used separately or in combination.
Examples of anionic stabilised polyurethane-based binders which are suitable as a component of the aqueous binder module in which (meth)acrylic copolymers and polyurethane resin, bonded covalently or in the form of interpenetrating resin molecules, are present are described, for example, in EP-A-353 797, EP-A-297 576, DE-A-41 22 265 and DE-A-41 22 266. These are polymer hybrids which are prepared by emulsion polymerisation of radically polymerisable monomers in the presence of anionic stabilised polyurethanes which optionally -carry unsaturated functions.
These are preferably the type of polyurethane based binder described in DE-A-41 22 265.
These are polyurethane dispersions, prepared by radical-initiated polymerisation of polyurethane macromonomers with a proportion of carboxyl, phosphonic acid or sulphonic acid groups and lateral vinyl groups as well as optional terminal vinyl groups, hydroxyl, urethane, thiourethane and/or urea groups.
These polyurethane dispersions may, in principle, be prepared by a variety of methods. One method comprises, e.g. preparing a polyaddition product by polyaddition of polyhydroxy compounds from the group polyhydroxy-polyethers, polyhydroxy-polyesters and polyhydroxy-polycarbonates, also polyhydroxycarboxylic acids, dihydroxyphosphonic acids or ;~ ~ ;
.
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polyhydroxysulphonic acids as well as polyisocyanates and a monomer which contains at least two hydroxyl groups and at least one vinyl group. The proportions of reactants, in particular of polyisocyanate, are selected so that a macromonomer with terminal hydroxyl groups is produced. This macromonomer, which in addition contains carboxyl, phosphonic acid or su~phonic acid groups and lateral vinyl groups, is then neutralised, if the acid groups in the monomers which contained these groups were not used initially in the neutralised form.
To prepare the polyurethane dispersion, the macromonomers thus obtained, which contain vinyl groups, are converted into an aqueous dispersion by the addition of water and polymerised by radical-initiated polymerisation using methods which are known per se. During this polymerisation, if so-called reactive diluters are not present from the start, monomers are added which are then co-polymerised into the polyurethane.
These monomers are alpha,beta-unsaturated monomers. Examples of these are alpha,beta-unsaturated vinyl monomers such as alkylacrylates, -methacrylates and -crotonates with 1 to 20 carbon atoms in the alkyl chain, di-, tri- and tetraacrylates, -methacrylates and -crotonates of glycols, tri- and tetra-functional alcohols, substituted and unsubstituted acryl- and methacrylamides, vinylethers, alpha,beta-unsaturated aldehydes and ketones, vinylalkyl ketones with 1 to 20 carbon atoms in the alkyl chain, vinyl ethers, vinylesters, diesters of alpha,beta-unsaturated dicarboxylic acids, styrene, styrene derivatives, such as e.g, alpha-methylstyrene.
The polyurethane paste resins which are mentioned above, e.g.
from DE-A-40 00 889, may also be used as anionic stabilised PU resins in the aqueous binder module B) according to the invention. These are urethanised oil-free polyesters which '''~
' .
~21~4035 contain OH groups, prepared by reacting diisocyanates with an excess of a polyol mixture and lower molecular dialcohols, of which some also contain at least one acid group capable of forming an anion. The number average of the molecular mass of these PU binders is preferably 3000 to 200000, particularly preferably less than 50000.
The binder module B) needed to prepare aqueous base lacquers may consist of one aqueous binder. The aqueous binders may also, however, be present in combination. Thus, the binders are each prepared separately and stored as a single module afterwards or they are prepared as a mixture of binders and then stored as a multi-component binder module.
The binder module B) preferably contains aqueous binders based on anionic stabilised polyurethanes. It may be expedient, if some, e.g. up to 50 wt.% of the PU binder, is replaced by resins based on a combination of (meth)acrylic copolymer and polyester resin.
Furthermore, binder module B) may contain water-dilutable binders based on cellulose.
Aqueous binder module B) may also contain amino resins and/or blocked polyisocyanates. The amino resins and blocked polyisocyanates may be water-dilutable or non-water-dilutable and are commented on under the description of the cross-linking module. They are present in a ratio of 40 : 60 to 5 : 95 with respect to the water-dilutable binder, each being with reference to the solid resin.
I I
Rheology regulating agents may also be contained.
Furthermore, the aqueous binder may contain small proportions of conventional solvents, preferably less than 5 wt.%. These may be the water-miscible solvents described for the special effect module. The solids content of the binder module is preferably 20 to 60 wt.%.
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The binder module B) may contain neutralisation agents for the anionic resins. Bases are used for this. Examples are ammonia or organic amines such as triethylamine, N-methylmorpholine, aminoalcohols such as dimethyl-isopropanolamine, dimethylethanolamine, 2-amino-2-methylpropanol-l.
Aqueous binder module units which contain anionic resins have a pH of 7.0 - 8.5. The ratio of organic solvent to water in the aqueous binder module is up to 0.3 : 1, preferably less than 0.2 : 1.
The modular system (made from modules A) and B)) used according to the invention may also include at least one aqueous dye module C), which contains, in addition to at least one anionic and/or non-ionic stabilised water-dilutable ~-binder, dye pigments and/or fillers and optionally additives.
Each dye module C) preferably contains not more than 4 different dye pigments and/or fillers, particularly preferred aqueous dye modules being those which contain only one dye pigment or only one filler. Examples of inorganic or organic dye pigments or fillers which can be used in the dye module are titanium dioxide, micronised titanium dioxide, iron oxide pigments, carbon black, silicon dioxide, barium sulphate, micronised mica, talc, azo-dyes, phthalocyanin dyes, quinacridone or pyrrolopyrrole pigments.
The same water-dilutable anionic and/or non-ionic stabilised resins may be used as described for the binder module. These are preferably binders which carry an anionic charge which act!as binder components in the final special effect base lacquer. The resins may be based on polyesters, acrylates or polyurethanes. The resins may be paste resins alone or in combination with film-forming binders or cross-linking agents. PU paste resins, as described in DE-A-40 00 889, are particularly preferred.
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~114035 Each aqueous dye module C) preferably contains the same binder or mixture of binders. In addition, water-dilutable or non-water-dilutable cross-linking component~ may be contained in the dye module.
Furthermore, the dye module C) may contain small proportions of water-miscible solvents. Bases may also be contained as neutralisation agents. It may be convenient if dye module C) contains rheology regulating agents. Furthermore, conventional lacquer additives, such as e.g. wetting agents, defoamers and flow controllers, may be contained in aqueous dye module C).
The aqueous dye modules C) are generally prepared in such a way that the dye pigment or filler is ground into some of the aqueous binder or preferably into a paste resin. This takes place in equipment which is known to the person skilled in the art. Afterwards, the remaining amount of water-dilutable resin is added. This may be the same or a different binder from that used in the dispersing stage.
Aqueous, storage-stable dye modules C) are produced with a pigment/binder ratio of 0.01 : 1 to 10 : 1. The solids content is preferably 20 to 80 wt.%.
Dye modules which contain anionic resins have a pH of 7.0 to 10Ø The ratio of organic solvent to water in the aqueous dye modules is up to 0.3 : 1, preferably up to 0.2 : 1.
The modular system used according to the invention may contain a rheology module D). This contains water and one or more substances which regulate the flow behaviour of the final special effect base lacquer as a rheology component.
Examples of these are polymeric microparticles, such as are described, for example, in EP-A-38 127, inorganic sheet silicates, e.g. aluminium magnesium silicate, sodium r', ., .` . , r': ~ :
'' .~', 0 3 ~
magnesium sheet silicate and sodium magnesium fluorolithium sheet silicates of the montmorillonite type, associative thickeners, based on e.g. polyurethane or cellulose, polyvinylalcohols, synthetic polymers with ionic groups such as e.g. poly(meth)acrylic acid. These substances are commercially obtainable in a variety of forms.
. , The modular system used according to the invention may also contain a cross-linking module E). The cross-linking module E) is used in particular when the final aqueous special effect base lacquer being produced is being prepared with the use of resins which contain cross-linkable groups in the molecule.
Examples of cross-linking resins contained in the cross-linking module are amino resins and/or blocked isocyanates. -These are partially or completely etherified amine/
formaldehyde condensation resins and/or blocked polyisocyanates with at least two reactive sites per molecule. -Such amino resins are described, for example, in Ullmann's "Encyclopedia of Industrial Chemistry", 5th ed., vol, A2, chapter "Amino resins", pages 115 - 141 (1985) and Houben- ~ -Weyl, "Methoden der Organischen Chemie", vol. 14/2, pages 319 - 388 (1962). The resins are prepared according to the prior art and supplied by many firms as commercial products.
~ ~ .
Examples of such amino resins are amine/formaldehyde condensation resins which are produced by the reaction of aldehydes wlth melamine, guanamine, benzoguanamine or dicyanodiamide. The alcohol groups in the aldehyde condensation products are then partially or completely etherified with alcohols.
Examples of blocked isocyanates are any di- and/or ~ `
polyisocyanates in which the isocyanate groups have been : ,.,,.~-.
- ., .
17 2~ 3~
reacted with a compound which contains active hydrogen.
Appropriate prepolymers which contain isocyanate groups may also be used as di- and/or polyisocyanates. The organic di-and/or polyisocyanates have an average molecular weight of 112 to 2000 and expediently an average isocyanate functionality of 2 to 8. These are e.g. aliphatic, cycloaliphatic, aromatic, optionally also sterically hindered polyisocyanates. So-called "lacquer polyisocyanates" which are prepared from known diisocyanates are particularly suitable as polyisocyanates.
Typical examples of this type of polyisocyanate are propylene diisocyanate, tetramethylxylylene diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, trimethylhexane diisocyanate, cyclohexene-1,3 and -1,4 diisocyanate, methylcyclohexane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate or dicyclohexylmethane ~-diisocyanate.
Isocyanates which are convenient to use are polyisocyanates which also have urethane groups, which can be obtained by reacting excess amounts of diisocyanate with simple polyhydric alcohols with a molecular weight of 62 to 300, especially trimethylolpropane.
Lower molecular weight compounds for blocking NCO groups are ~ -known. Examples of these are aliphatic or cycloaliphatic alcohols, dialkylamino alcohols, oximes, lactams, imides, hydroxyalkyl esters, malonates or acetoacetates.
The cross-linking module may contain the cross-linking agent alone. However, it may also contain one or more organic solvents, water, one or more anionic and/or non-ionic stabilised, water-dilutable binders and/or one or more conventional lacquer additives. These are, for example, the same as those described for the other modules.
:. . -: ,:
' , ..... ' : ~ . . , .
18 ~1~403~
The different modules are storage-stable. They may be u~ed in the modular system according to the invention. Furthermore, it is possible to mix several identical or different modules to give new storage-stable combination modules. For example, different special effect and/or dye modules may be mixed.
Likewise, cross-linking modules and binder modules may be mixed. Likewise, the rheology module may be mixed with the special effect or the dye module. It has been shown to be expedient to select a modular system for mixing coating agents in which the special effect module and binder module and optionally the dye module are kept as separate entities.
The rheology and/or cross-linking module may be present as separate entities or mixed with the other modular units.
The aqueous single component special effect base lacquer is prepared by simply mixing the special effect module with the binder module and optionally the dye module and/or the rheology module and/or the cross-linking module. Any sequence may be used for admixing, preferably, however, the module with the highest viscosity and the largest share of the volume is initially introduced. After mixing well, the application viscosity is adjusted by the addition of deionised water.
The final special effect base lacquer prepared according to ~ ~;
the invention has a solids content of preferably 10 -40 wt.%, partiaularly preferably 15 - 30 wt.%, with a pigment/binder ratio of 0.06 : 1 to 0.6 : 1. The resin composition in the lacguer solids is preferably kept constant in each individual special effect base lacquer, wherein in thelcase of those special effect base lacquers which contain cross-linking agents there is a ratio of film-forming binder to cross-linking resins of 95 : 5 to 60 : 40 within the solid resin composition.
The proportion of solvent is less than 20 wt.%, preferably less than lO wt.%. The pH of the aqueous base lacquer is the ;
' ' ~
: ,...
19 '~1~ 4~3~
result of mixing the modular units. A correction to the pH i8 generally not required.
The final aqueous special effect base lacquer may be applied directly after mixing, but if may also be stored for longer than 12 months.
The aqueous special effect base lacquers prepared according to the invention may be applied using conventional methods.
They are preferably applied by spraying in a dry layer thickness of 10 - 25 ~m and processed using a wet-on-wet method, that is they are over-lacquered after an evaporation phase at 20 - 80C, using a conventional clear lacquer in a dry layer thickness of preferably 30 - 60 ~m, and dried or cross-linked in common with this at temperatures between 20 ~-and 140C.
The multi-layered special effect lacquers obtained in this way correspond to the currently conventional requirements for motor vehicle lacquers. The aqueous special effect base lacquers prepared according to the invention are thus suitable for lacquering vehicles and vehicle repairs, but they may also be used in other areas, such as e.g. lacquering plastics, in particular for lacquering motor vehicle parts.
The modular system used according to the invention consists of individual storage-stable modules. The modules contain film-forming binders which can be prepared in solvent form or in the agueous phase. Low-solvent, aqueous, special effect base lacquers which have good long-term storage stability, canlbe prepared using the modular system used according to the invention, In particular, efficient storage and production of the aqueous special effect base lacquer is achieved.
The following examples explain the invention. All parts (P) refer to parts by weight.
; , .
~ 35 Example 1 Preparation of a PU dispersion in accordance with DE patent application P 42 24 617, which is not yet laid open to public inspection, preparation example 3:
1005 g of a linear polyester (formed from adipic acid, isophthalic acid and hexanediol with an OH value of 102) are heated to 90C in a reaction vessel with a stirrer, internal thermometer, heat-supply and reflux condenser and 1.8 g of trimethylolpropane and 393 g of isophorone diisocyanate are added at this temperature. The mix is held at this temperature until the NCO value is 3.8. After cooling to ~ -60C, a solution of 35.3 g of dimethylolpropionic acid, 26.1 g of triethylamine and 250 g of N-methylpyrrolidone are added. After heating to 80C, the temperature is kept ~ -constant until an NCO value of 1.5 is reached. The molar amount of deionised water is admixed and the solution is held at 80C until isocyanate can no longer be detected. Finally, the mix is diluted with enough water to produce a liquid dispersion with a solids content of 34 wt.%.
., .
Example 2 ' -.
Preparation of a special effect module A
.
The following components are contained in the special effect module:
.`'' ' .
32.0 parts of a conventional polyurethane dispersion (in accordance with DE-A-4122265, example 1) with 35 wt.%
SC (SC = solids content), 13.4 parts of a commercially available aluminium paste containing 60 % aluminium, suitable for water base lacquers, 1.3 parts of an aluminium wetting additive based on organic phosphoric acid derivatives, ?~
21 ~114035 7.7 parts of n-butanol, 3.3 parts of a commercially available thickener based on polyacrylic acid, 3.3 parts of N,N-dimethylethanolamine.
The aluminium paste is initially introduced and mixed into a slurry with the solvent and additives. The binder is then added and mixed well.
Example 3 Preparation of a special effect module B
35 parts of the PU dispersion from example 1, 20 parts of the aluminium paste from example 2, 2 parts of the wetting additive from example 2, 25 parts of butyl glycol, 1.8 parts of the thickener from example 2 and 0.2 parts of N,N-dimethylethanolamine are processed using the same method as in example 2. Afterwards, the mixture is diluted with 16 parts of deionised water.
Example 4 PrepaFation of a binder module A
The following components are well mixed toqether with stlrring:
;::
42.0 parts of a conventional polyurethane dispersion (in accordance with DE-A-4122265, example 1) with 35% SC, 47.0 parts of completely demineralised water, 2.3 parts of n-butanol, 6.0 parts of butyl glycol, 1.4 parts of a commercially available thickener based on polyacrylic acid, 1.3 parts of N,N-dimethylethanolamine.
:, ,~
-22 '~ 4 0 3 ~
Example 5 Preparation of a binder module B
26.2 parts of the PU dispersion from example 1, 8.8 parts of hexamethoxymethylmelamine, 5 parts of n-butanol, 3.5 parts of the thickener from example 2, 0.25 parts of N,N-dimethylethanolamine and 56.25 parts of deionised water were mixed together in the same way as in example 4.
Example 6 Preparation of a blue dye module A
The dye module contains the following components:
42.0 parts of a conventional polyurethane paste resin (in accordance with DE-A-4000889) with 35~ SC, 34.0 parts of a commercial blue copper phthalocyanine pigment, 5.0 parts of a dispersion aid (Disperse Ayd W22), 18. 85 parts of completely demineralised water, 0.15 parts of N,N-dimethylethanolamine.
First, the pigment is made into a slurry in a mixture of additives and about half of the paste resin. Then the rest of the paste resin, amine and water are added and well mixed.
':
Example 7 Preparation of a green dye module B
45 parts of the paste resin from example 6, 30 parts of a commercially available green phthalocyanine pigment, 5 parts of the dispersion aid from example 6, 2 parts of butyl glycol, 17.9 parts of deionised water and 0.1 parts of N,N-^ 211403~
dimethylethanolamine are processed in the same way as inexample 6.
Example 8 Preparation of aqueous special effect base lacquers Storage-stable special effect base lacquers are prepared by smoothly stirring together the modules cited in the Table:
SPECIAL EFFECT BASE LACQUERS
A (~ilver B (~ilver C (blue D ( green metallic) metallic) metallic) metallic) 8inder module A 70 P 60 P
Binder module B 80 P 75 P
Sp. effect mod. A 30 P 20 P
Sp. effect mod. B 20 P 15 P
Dye module A 20 P
Dye module B
P = parts by weight ;
.: . . . ~
Claims (13)
1. A process for preparing aqueous coating agents with adjustable optical effects, by mixing at least two storage-stable, pre-mixed, aqueous modules, characterised in that A) at least one aqueous special effect module containing one or more special effect pigments, one or more anionic and/or non-ionic stabilised water-dilutable binders, one or more organic solvents, at least 20 wt.% of water and optionally conventional lacquer additives, and B) at least one binder module containing one or more anionic and/or non-ionic stabilised water-dilutable binders, water, and optionally one or more organic solvents, one or more cross-linking agents and/or conventional lacquer additives are mixed together.
2. A process according to Claim 1, characterised in that a special effect module A) is used which contains metallic pigments and/or interference pigments as special effect pigments.
3. A process according to Claim 1 or 2, characterised in that a special effect module A) is used which contains anionic stabilised binders at a pH of 7.0 to 9Ø
4. A process according to Claims 1, 2 or 3, characterised in that a special effect module A) is used which contains exclusively metallic pigments as special effect pigments, wherein the metallic pigment content is 3 to 13 wt.%, with reference to the total weight of the components in the special effect module, with a pigment/binder ratio of 0.02 : 1 to 10 : 1, with reference to the weight of solids and at a pH of 7.2 to 8Ø
5. A process according to Claim 4, characterised in that the special effect module contains metallic pigments based on water-sensitive metals such as aluminium and steel.
6. A process according to Claim 4 or 5, characterised in that a special effect module based on one or more anionic stabilised binders is used.
7. A process according to one of the preceding Claims, characterised in that several special effect modules are used, each of which contains the same binder or mixture of binders.
8. A process according to one of the preceding Claims, characterised in that one or more special effect modules with a water content of at least 50 wt.% are used.
9. A process according to one of the preceding Claims, characterised in that the special effect module A) and/or the binder module B) contains one or more binders based on polyurethane resins.
10. A process according to one of the preceding Claims, characterised in that, in addition to special effect module A) and binder module B) C) at least one dye module containing one or more pigments and/or fillers, one or more anionic and/or non-ionic stabilised water-dilutable binders, water, and optionally one or more organic solvents and/or conventional lacquer additives, and/or D) at least one rheology module containing one or more organic or inorganic agents for regulating rheology and water, and optionally one or more anionic and/or non-ionic stabilised water-dilutable binders and/or one or more organic solvents, and/or E) at least one cross-linking module containing one or more cross-linking agents, and optionally one or more organic solvents, water, one or more anionic and/or non-ionic stabilised water-dilutable binders and/or one or more conventional lacquer additives, are used.
11. A process according to Claim 10, characterised in that the dye module C) has a solids content of 20 to 80 wt.%.
12. A process according to one of Claims 10 or 11, characterised in that the cross-linking module E) contains one or more blocked isocyanates and/or one or more amine resins as cross-linking agents.
13. A process according to one of the preceding Claims, characterised in that the modules are mixed in proportions such that a coating agent which contains less than 20 wt.% of organic solvent is produced.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4301991.9 | 1993-01-26 | ||
DE4301991A DE4301991A1 (en) | 1993-01-26 | 1993-01-26 | Modular system and its use in processes for the production of aqueous coating compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2114035A1 true CA2114035A1 (en) | 1994-07-27 |
Family
ID=6478900
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002114035A Abandoned CA2114035A1 (en) | 1993-01-26 | 1994-01-24 | Process for preparing aqueous coating agents using modular systems |
Country Status (10)
Country | Link |
---|---|
US (1) | US5672649A (en) |
EP (1) | EP0608773B2 (en) |
JP (1) | JPH06340830A (en) |
AT (1) | ATE167509T1 (en) |
CA (1) | CA2114035A1 (en) |
DE (2) | DE4301991A1 (en) |
DK (1) | DK0608773T3 (en) |
ES (1) | ES2118267T3 (en) |
GR (1) | GR3027607T3 (en) |
MX (1) | MX9400678A (en) |
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US6555612B1 (en) | 1999-01-28 | 2003-04-29 | Basf Coatings Ag | Aqueous coating material and modular system for producing same |
US6630211B1 (en) | 1999-02-25 | 2003-10-07 | Basf Coatings Ag | Utilization of tricyclodecandimethanol for producing multilayer lacquers |
US7923113B2 (en) | 2005-12-15 | 2011-04-12 | Akzo Nobel Coating International B.V. | Multilayer coating system |
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MXPA01001665A (en) * | 2000-02-18 | 2002-04-01 | John Michael Friel | PAINTINGS FOR THE MARKING OF ROADS, PREPARED FROM PREPINTURES; METHOD AND APPARATUS FOR FORMING ZONES AND LINES MARKED ON THE ROADS, WITH SUCH PAINTS AND DEVICE FOR APPLYING SUCH PAINTS |
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US7652099B2 (en) † | 2005-09-12 | 2010-01-26 | E.I. Du Pont De Nemours And Company | Process for producing coating compositions with customizable properties |
DE102005054867A1 (en) * | 2005-11-17 | 2007-05-24 | Basf Coatings Ag | Physically, thermally and physically and thermally curable, metallic effect-containing, aqueous mixtures, process for their preparation and their use |
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DE3333073A1 (en) * | 1983-09-14 | 1985-03-21 | Herberts Gmbh, 5600 Wuppertal | METHOD FOR THE PRODUCTION OF STORAGE-CONCENTRATES AND THE USE THEREOF FOR THE PRODUCTION OF COATING AGENTS |
AT381499B (en) * | 1985-02-27 | 1986-10-27 | Vianova Kunstharz Ag | WATER-DISCOVERABLE COATING AGENTS, METHOD FOR THE PRODUCTION AND THEIR USE FOR BASE LAYERS WITH TWO-LAYER TOP COATING |
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US5104922A (en) † | 1990-10-22 | 1992-04-14 | E. I. Du Pont De Nemours And Company | Stable aqueous aluminum flake dispersion |
JPH04234464A (en) * | 1990-12-10 | 1992-08-24 | Basf Corp | Base coat composition for automobile paint and method for forming the composition |
DE4107136A1 (en) * | 1991-03-06 | 1992-09-10 | Basf Lacke & Farben | METHOD FOR PRODUCING A MULTILAYER, PROTECTIVE AND / OR DECORATIVE PAINT |
US5236995A (en) * | 1991-03-26 | 1993-08-17 | Basf Corporation | Post-extended anionic polyurethane dispersion |
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-
1993
- 1993-01-26 DE DE4301991A patent/DE4301991A1/en not_active Withdrawn
-
1994
- 1994-01-21 ES ES94100827T patent/ES2118267T3/en not_active Expired - Lifetime
- 1994-01-21 AT AT94100827T patent/ATE167509T1/en active
- 1994-01-21 DE DE59406245T patent/DE59406245D1/en not_active Expired - Lifetime
- 1994-01-21 DK DK94100827T patent/DK0608773T3/en active
- 1994-01-21 EP EP94100827A patent/EP0608773B2/en not_active Expired - Lifetime
- 1994-01-24 CA CA002114035A patent/CA2114035A1/en not_active Abandoned
- 1994-01-25 JP JP6006118A patent/JPH06340830A/en active Pending
- 1994-01-25 MX MX9400678A patent/MX9400678A/en unknown
-
1996
- 1996-09-04 US US08/707,268 patent/US5672649A/en not_active Expired - Lifetime
-
1998
- 1998-08-07 GR GR980401785T patent/GR3027607T3/en unknown
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5824733A (en) * | 1994-04-30 | 1998-10-20 | Wacker-Chemie Gmbh | Aqueous coating product and a process for producing multiple layer paint coatings whose perceived color varies with the angle from which they are viewed |
US6555612B1 (en) | 1999-01-28 | 2003-04-29 | Basf Coatings Ag | Aqueous coating material and modular system for producing same |
US6630211B1 (en) | 1999-02-25 | 2003-10-07 | Basf Coatings Ag | Utilization of tricyclodecandimethanol for producing multilayer lacquers |
US7923113B2 (en) | 2005-12-15 | 2011-04-12 | Akzo Nobel Coating International B.V. | Multilayer coating system |
Also Published As
Publication number | Publication date |
---|---|
GR3027607T3 (en) | 1998-11-30 |
MX9400678A (en) | 1994-08-31 |
EP0608773B2 (en) | 2008-08-20 |
EP0608773B1 (en) | 1998-06-17 |
DK0608773T3 (en) | 1999-04-06 |
US5672649A (en) | 1997-09-30 |
JPH06340830A (en) | 1994-12-13 |
DE59406245D1 (en) | 1998-07-23 |
ATE167509T1 (en) | 1998-07-15 |
ES2118267T3 (en) | 1998-09-16 |
DE4301991A1 (en) | 1994-07-28 |
EP0608773A1 (en) | 1994-08-03 |
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